US3775130A - Photosensitive material comprising benzopyrylium dye sensitizer - Google Patents

Photosensitive material comprising benzopyrylium dye sensitizer Download PDF

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US3775130A
US3775130A US3775130DA US3775130A US 3775130 A US3775130 A US 3775130A US 3775130D A US3775130D A US 3775130DA US 3775130 A US3775130 A US 3775130A
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resinous binder
photosensitive material
vinyl
group consisting
binder solution
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T Enomoto
T Kawanishi
A Yasumori
T Shiga
Y Hirosawa
T Kubota
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Ricoh Co Ltd
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/675Compositions containing polyhalogenated compounds as photosensitive substances
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031Organic compounds not covered by group G03F7/029
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055Radiation sensitive composition or product or process of making
    • Y10S430/114Initiator containing
    • Y10S430/116Redox or dye sensitizer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055Radiation sensitive composition or product or process of making
    • Y10S430/127Spectral sensitizer containing

Abstract

A photosensitive material for producing a photographic recording material, comprising a resinous binder solution containing dispersed therein a photo-polymerizable N-vinyl monomer, a photoactive agent and a dye sensitizer, said dye sensitizer consisting essentially of a salt selected from the group consisting of (1) a benzopyrylium salt and (2) a double complex salt consisting essentially of said benzopyrylium salt and a decolorized derivative of said benzopyrylium salt.

Description

United StatesPatent 191v Enomoto et al.

[451 Nov. 27, 1973 PHOTOSENSITIVEMATERIAL COMPRISING BENZOPYRYLIUM DYE SENSITIZER Inventors: Takamiti Enomoto; Toshiyuki Kawanishi; Akiyoshi Yasumori; Tsuyoshi Shiga; Yujiro Hirosawa; Tomio Kubota, all of Tokyo, Japan Assignee: Ricoh, Co., Ltd., Tokyo, Japan Filed: Dec. 23, 1971 Appl. No.: 211,743

Foreign Application Priority Data Dec. 28, 1970 Japan 45/l25987 US. Cl. 96/90 R, 96/1l5 P, 204/159.23 Int. Cl G03c 1/70 Field of Search 96/1 15 P, 90 R;

References Cited UNITED STATES PATENTS 3/l970 Yamada et al. 96/90 R 3,600,179 8/1971 Yamada et al 96/90 R 3,607,266 9/1971 Yamada et al l. 96/90 R 3,300,314 l/l967 Rauner et al. 96/90 R Primary Examiner-Ronald H. Smith Att0rneyHenry T. Burke et al.

[5 7] ABSTRACT benzopyrylium salt.

6 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material for producing a photographic recording material useful in the reproduction of an original image thereon by photopolymerization.

2. Description of the Prior Art It is widely known to form photographic images by reactions caused by the effect of a light. Particularly a research on photo polymerization has of late been conducted wherein free radicals are produced by means of irradiation by the light and these free radicals cause the polymerization of certain kinds of monomers. Based upon such research, applications in the field of image forming have been developed, for instance, an applica-- dye sensitizer, which I promotes the photopdlym erization, in a proper resinous binder solution. Either a positive or negative image can be formed on thus prepared photographic recording material by exposure to a mercury lamp as a light after having been fixed with a desired proper original image laid thereon, and then by being subjected to the heat treatment. According to the U.S. Pat. No. 3,503,745 specification and the Japanese Patent Publication No. 45-13258, for instance, photographic recording materials are specified, wherein, as for the monomer used in the preparation of photosensitive layer, a vinyl monomer (for instance, vinyl-carbazole and vinylindole) comprising a heterocyclic ring which has at least one nitrogen atom in its composing molecules is used; as for the photo-active agent, an aliphatic hydrocarbon halide (for instance, carbon, tetrabromide, ethane hexabromide, .bromo form, iodoforrn, etc.),is used; and as for the binder, such natural water soluble high polymeric substances as gelatin, casein, gum arabic, etc., such synthetic water soluble high polymeric substances as polyvinyl alochol, polyacrylic acid, polyamide, etc., and copolymer of styrene-acrylic nitrile. The dye sensitizers which have hitherto been sugested to be used in the photosensitive layer of such photographic recording materials as mentioned above are generally obtainable on the market and include the following dyes: triphenylmethyl dyes (such as Malachite Green, Crystal Violet, etc), Rhodamine B, Eosine B, Cyanin dyes (such as pinacyanol, Ethyl Red, Quinaldine Red, etc.), Styryl dyes [4- (p-dimethylaminostyryl )quinoline, etc. Acridine dyes, Thiazine dyes, etc. Rhodamine B- and Styryl dyes are said to be most satisfactory. However, the perfumance of the aforementioned dye sensitizers are not completely satisfactory in meeting the requirements of photographic recording materials.

SUMMARYOF THE INVENTION The present invention provides photosensitive materials for producing photographic recording materials having improved properties due to the use of novel dye sensitizers.

The dye sensitizers utilized in the photosensitive products of the present invention are salts selected from the group consisting benzopyrylium salts having a chemical structure expressed by formula-(I) and double complex salts formed as reaction products of said benzopyrylium salts and decolorized derivatives thereof having a chemical structure expressed by the formula-(II).

Formula-(I) Ra 0 RI (Y),,'

| (gig R2 I R4 wherein X is a radical selected from'the group consisting of hydrogen, halogen, nitro radical and nitrile radical;

Y is a radical selected from the group consisting of hydrogen, halogen, nitro radical, nitrile radical and carboxyl; radical;

R is a radical selected from the group consisting of hydrogen and alkyl radicals having I to 4 carbon atoms; 1 y

R is a radical selected from the group consisting of hydrogen and phenyl radical;

R and R each is a radical selected from the group consisting of hydrogen, alkyl radicals having 1 to 2 carbon atoms and alkoxyl radicals having I to 2 carbon atoms; n and n each is an integer of l to 2; and Z is an anionic functional group.

Formula-(II) 0 R1 H on. l liza- H oona wherein X, Y, R,, R R R,,, n and n each is identical with that of the aforesaid formula-(I).

These dye sensitizers comprising a benzopyrylium salt or a double complex salt consisting essentially of said benzopyrylium salt and its decolorized derivative have properties which remarkably contribute to the improvement of photo sensitivity of the photosensitive layer extending over a very wide region of wave length ranging approximately from 400 my. to 800 mu. They are crystalline substances which are violet bluish violet blue in color when dissolved in an organic solvent.

A benzopyrylium salt having a chemical structure expressed by the formula-(I), which can be used as a dye sensitizer by itself and'a partner component of a complex dye sensitizer as well, is synthetically prepared as described below:

The benzopyrylium salt having the formula-(I) is prepared by reacting a substituted 2-hydroxybenzaldehyde having the formula-(II'):

CHO

(X); where R X and n are as defined above with an acetone derivative having the formula-(III) where R, and R are the same radicals as R, and R in the formula-(l), in an acid reaction solvent at l 30C, preferably at 0 20C, and thereafter reacting the reaction product in the same reaction system with an aldehyde having the formula (IV) where R,,, Y and n are as defined above and then by adding an acid having the desired anion functional group to the same reaction system. Of the aforementioned series of reactions, the reaction which takes place between the compounds having respectively the formula-(II') and (Ill) forms an aldehyde acetone derivative having the formula resonance structure with the formula-(V) where R,, R R X and n are as defined above. By adding aldehyde having the formula-(IV) to the previous product, a condensation cyclic reaction takes place. As for the mineral acid, hydrochloric acid is used; and for the solvent, such organic acids as formic acid, acetic acid, etc., are used. The quantity of the mineral acid added in this reaction is from 2 to 6 moles per mole of substituted 2-hydroxybenzaldehyde. I

The anionic functional group which corresponds to Z in the formula-(I) can be obtained either by selecting the acid which is introduced at the time of the condensation cyclic reaction or by reacting an acid or a salt having the desired functional group with the product mentioned above. Typical acids or salts for this reaction include perchloric acid, periodic acid, phosphoric acid, hydrochloric acid, sulfuric acid, oxalic acid, sodium borofluoride, potassium iodide, sodium iodide, potassium bromide, sodium bromide, dimethylphos-- phate, diphenylphosphate, etc.

Compounds within the scope of formulas (II), (III) and (IV) are obtained by known methods and are also available commercially. For instance, the substituted 2-hydroxybenzaldehyde having the formula-(ll') can be readily prepared, either by chlorinating or brominating the corresponding aldehyde or by formylating phenols. The substituted 2-hydroxybenzaldehyde thus prepared may be reacted with the acetone derivative having the formula-(Ill) in a mixed acid consisting of acetic acid and formic acid, or with the addition of any of the aforementioned acids, in the presence of a mineral acid or acids. The over-all reaction required for the preparation of the benzopyrylium salts can be conducted in succession in one reactor at room temperature.

The decolorized derivatives which form the double complex salts of the present invention are prepared by refluxing a benzopyrylium salt of formula-(l), in an alkaline solvent, for instance, a mixed solvent of methanol-benzene containing sodium bicarbonate. The solution is then concentrated and the reaction product is poured into a mixture of crashed ice and water to precipitate the crystals. The amount of alkali such as sodium bicarbonate and sodium carbonate employed is from 60 to wt. percent based on the weight of the reactants.

Since more than 1 liter of methanol is required to dissolve about 10 g of the benzopyrylium salt having the fonnula-(l), the subsequent reactions are necessarily conducted in a large reactor and the method presents many difficulties in separating the reaction product from the solvent. However, with the use of the aforementioned mixed solvent, the reaction of fonn the decolorized derivative can be readily conductedin a small quantity of reaction solvent thus avoiding many of the difficulties.

The double complex salt consisting essentially of the benzopyrylium salt and its decolorized derivative is prepared by means of a chemical reaction wherein the decolorized derivative obtained according to the aforementioned method and indicated by the formula-(ll) is admixed with the benzopyrylium salt having the formula-(I) and reacted in a suitable solvent. The resultant double complex salt demonstrates excellent sensitivity when used in the photosensitive materials. Reaction solvents utilized in combining a decolorized den'vative having the formula-( ll) with a benzopyrylium salt having the formula-(l), may be selected from the group consisting of dichloroethane, toluene, xylene and tetrahydrofuran. The reaction takes place under reflux conditions at a temperature from 50 to C, preferably at 50 60C. After completion of the reaction, the solvent is removed by distillation under reduced pressure and the reaction product is added to ether to precipitate the desired crystalline product.

The following detailed explanation illustrates the synthesis of benzopyrylium salts and their decolorized derivatives.

EXAMPLES OF SYNTHESlZlNG THE BENZOPYRYLIUM SALTS A. Synthesis of 2-p-methoxystyryl-3-phenyl-6- chlorobenzopyrylium perchlorate having the formula:

12 g of 2-hydroxy-5-chloroben'zaldehyde Cl CHO was added to l l g of phenylacetone and was dissolved with the use of 45 ml of formic acid. 30 ml of 35 percent hydrochloric acid was added to this solution with swirling at a room temperature over a period of 20 30 minutes. After the completion of the addition, the stirring was continued for another two hours and then 12 g of p-anisaldehyde and 50 ml of formic acid were added. ml of 35 percent hydrochloric acid was added dropwise over a period of. about 20 minutes. The mixture was stirred for an hour and was left standing overnight. The reaction mixture thus prepared was added dropwise to 180 ml of 15 percent l-lClO which had been cooled to 10C or below with stirring during a period of about 2 hours. The resultant precipitate was filtered by suction and was washed with 300 400 ml of ethyl ether. Recrystalization was effected with acetic acid to obtain 15 g of desired crystalline product. The melting point of this product ranged between 214 and 216C.

The absorption maximum wave length ()t max.) measured with the product in dichloroethane solution was 577 my.

B. Synthesis of 2-p-ch1orostyryl-3-pheny zopyrylium perchlorate having the formula:'

ben-

A mixture of 10 g of 2-hydroxybenzaldehyde CHO of this product was 211C and the measurement of its maximum wave length (A max) in dichloroethane solution showed the value of 5 l0 m,u..

C. Synthesis of 2-p-nitrostyryl-3-phenyl zopyrylium perchlorate having the formula:

A mixture of 10 g of 2-hydroxy-benzaldehyde benand 50 ml of formic acid were added, followed by the addition of, 10 ml of percent hydrochloric acid at room temperature over 20 minutes. The stirring was continued for one hour and the mixture was left standing overnight. The reaction mixture thus obtained was added to 180 ml of '15 percent HClO, which had been and 11 g of phenylacetone [CHSC o cmQ] was dissolved in ml of formic acid, into which soluand ml of formic acid were added to the preceding solution, and 10 ml of 35 percent hydrochloric acid was added at room temperature over a period of about 20 minutes. The stirring was then continued for one hour and the solution was left standing overnight. The reaction mixture was added to 180 ml of 15 percent HC]O,,

which had been cooled to 10C or below with stirring over a period of approximately two hours. The precipitate was filtered with suction and washed with 300 400 ml of ethyl ether, The desired crystalline product weighing 6 g in weight was obtained. The melting point A mixture I of 12 g chlorobenzaldehyde of 2 -hydroxy-5- and 11 g of phenylacetone was dissolved in 45 m1 of formic acid, and 30 ml of 35 percent hydrochloric acid was added at room temperature over a period of 20 30 minutes. After the addition was completed, stirring was continued for an additional two hours. Then 16 g of p-bromobenzaldehyde and 50 ml of formic acid were added, and 10 ml of 35 percent hydrochloric acid was dropped into the mix- 5 ture at room temperature over a period of approximately for 20 minutes. Another one-hour stirring followed and the mixture was left standing for one night. The reaction mixture thus prepared was added to 180 ml of 15 percent HClO which had been cooled to C or below with stirring for nearly two hours. The precipitate formed in the mixture and was recovered by suction. It was washed with 300 400 ml of ethyl ether. 4 g of the desired crystalline product having a melting point of 228 230C was obtained.

its absorption maximum wave length (A max) was 525 my" E. Synthesis of 2-p-cyanostyryl-3-phenyl-6- chlorobenzopyrylium perchlorate having the formula:

A mixture of 12 g of 2-phdroxy-5- chlorobenzaldehyde C1 CH0 and 11 g of phenylacetone c...cocm@ [NC-Q-CHO] and 100 ml of formic acid were added. 10 ml of percent hydrochloric acid was added dropwise at room temperature. This was followed by the one-hour stirring and the mixture was left standing overnight. The reaction mixture thus prepared was added to 180 ml of 15% HCIO, which had been cooled to 10C or below, with stirring over a period of about two hours. The precipitate thus formed was recovered by suction and 3.5 g of the desired crystalline product with a melting point of 212 214C was obtained. The product was dissolved in dichloroethane to measure its absorption maximum wave length (A max) which was 532 mp..

EXAMPLES OF SYNTHESlZlNG THE DECOLORIZED DERIVATIVES FROM THE BENZOPYRYLIUM SALTS A. Synthesis of 2-p-methoxystyryl 3-phenyl-4- methoxy-6-chloro-1.4-benzopyran having the formula:

8 TCH=CH0CHz l H OCHt 10.8 g of 2-p-methoxystyryl-3-phenyl-6- chlorobenzopyrylium perchlorate having the formula 0 Tom-.cnQ-ocm 01 0 010.-

and 15 g of sodium hydrogencarbonate were mixed with 50 ml of methanol and ml of benzene and the mixture was heated for about one hour, during which time the color of the reaction mixture turned from purple to yellow. After the reaction matter was cooled, it was subjected to the filtration by means of suction. The mother liquor was concentrated under reduced pressure. The residue was dissolved and extracted with methanol and was then poured into the mixture of crashed ice and water to separate the desired product as light yellow crystals which were recovered by suction and dried under reduced pressure after washing with water. The crystals thus obtained melted at 74 76C. The results of its elemental analysis were as follows:

theoretical values: H 5,19%, C 74.41%, Cl 8.78%

experimental values: H 5.32%, C 74.56%, Cl 8.50%

It absorption maximum wave length (A max) in dichloroethane solution was 420 mp. and the molar extinction coefficient was found to be 3.4.7 X 10'. The desired product was obtained almost quantitatively.

B. Synthesis of 2-p-chlorostyryl-3-phenyl-4-methoxy- 1.4-benzopyran having the formula:

o T CH=CHC1 H OCH:

10 g of 2-p-chlorostyry1-3-phenylbenzopyrylium perchlorate, I

0 CH=CHC1 k O 010.-

and 15 g of sodium carbonate was added to 50 ml of methanol and 100 ml of benzene and the mixture was heated for about one hour. The reactionmixture was cooled and filtered by suction. The filtrate was concentrated under decreased pressure. The residue was dissolved and extracted with methanol and was poured into a mixture of crashed ice and water, to separate the product as light yellow crystals. It was recovered by suction, washed thoroughly, and dried under decreased pressure to obtain 7.5 g of the desired product. The melting point of the crystals thus obtained was 705C. The results of elemental analysis were as follows:

theoretical values: H 5.07%, C 76.90%, Cl 9.48% experimental values: H 5.21%, C 76.83%, Cl 9.67%

perchlorate according to the method explained in the foregoing examples. To the yellow viscous liquid obtained by concentration under reduced pressure was added 4.2 g of 2-p-methoxystyryl-3-phenyl-6- The ab or tion m i wave l h (A 5 methoxybenzopyrylium perchlorate and 150 ml of di- Sured i di hl h l i was 310 m M and h chloroethane. The mixture was refluxed at 50 to 60C molar extin ti n ffi i t was 102 X for the period of five hours. About 100 ml of dichloro- C. Synthesis of 2-p-bromstyryl-3-phenyl-4-methoxyethane was then removed by reduced pressure distillah 4 having the formula; tion and the residual liquid (about 50 ml) was cooled 10 to room temperature. It was then mixed in small portions with approximately 300 ml of ether to separate 01 I crystals of the desired complex dye. The mixture was left standing for about 30 minutes and was filtered with suction. The cr stals were then dried under reduced H OCHa y V V pressure. I

g. of 2-p-bromstyryl-3-phenyl-6- The crystals thus obtained had a melting point of chlorobenzopyrylium perchlorate 208 210C and its dichloroethane solution was blue. 0 I When the spectral absorption spectrum was measured 1n dichloroethane solution of 1 X 10 mol/ml concen- 01F tration, the absorption maximum wave length (A max) was in the range between 581 mg and 657 m;;..

A number of the benzopyrylium salts having the formula-(I) as indicated in Table-1 and a number of the and 15 g of Sodium bicarbonate Were add d to 0. m decolorized derivatives having the formula( II) as indiof methanol and 100 ml of benz n and th m xtur cated in Table-lwere prepared according to the aforewas heated for one h'Our. The rea ti n miXt was said procedures. Additionally, a number of the double cooled, filtrated by suction, and the filtered was conom lex S lts s indicated with No. 1 to N0. 16 in Tacentrated under reduced pressure. The residue was disble-l were prepared by the following procedure. solved inmethanol and poured into a mixture of To the benzopyrylium salts were added each of the crashed ice and water to separate light yellow crystals. 3 concentrates (yellow viscous liquid substances) ob- The mixture containing the crystals was filtered with tained in the syntheses of the decolorized derivatives in suction. The precipitate was thoroughly washed, and the ratio of from 1.7 to 2.5 parts by weight per one part dried under reduced pressure to obtain the desired by weight of said benzopyrylium salt. The resultant crystalline product quantitatively, with a melting point mixtures were each added to 150 ml of dichloroethane of 80 82C. As the result of elemental analysis, the and then refluxed at the temperature between and following values were obtained: C for 5 hours. About ml of dichloroethane contheoretical values: H 3.97%, C 63.51%, Br 17.86%, tained in the respective reaction products were re- Cl 7.82% moved with reduced pressure distillation and the residexperimental value: H 3.75%, C 63.32%, Br 17.60%, ual liquids (about 50 ml) were each cooled to room Cl 8.06% I 40 temperature and then mixed in small portions with ap- The measurement made with the product dissolved in proximately 300 ml of ether to separate crystals of the dichloroethane showed that the absorption maximum desired double complex salts. The mixtures were left wave length (A max)was324jrnp and the molar extincstanding for about 30 minutes'and then filtered withtion coefficient 1.57 X 10". 45 suction. The crystals were then dried under reduced pressure. I EXAMPLES DOUBLE The double complex salts thus obtained and their properties are summarized in Table-l. The colors indi- A decolorized derivative was prepared from 10.8 g of cated in Table-l are colors of the dichloroethane solu-.

2-p-methoxystyryl-3-phenyl-6-chlorobenzopyryliumtions containing the aforesaid double complex salts.

TABLE 1 7 Compound structure Complex max Color of dye Compounds belonging to Formula (I) Compounds belonging to Formula (II) (m e/10 solution 1'. 2-p-methoxystyryl3-phenyl 6-chlorobenzopy- Diseolored 2-p-methoxystyryl-3-phenyl-fi meth- 538 2,34 g

ryliurn perchlorate. oxybenzopyryliurn perchlorate. 668 5. 82

2 2-p-methoxystyryl-3phenyl-6-methoxybenzopy- Discolored 2-p-methoxystyryl-3-phenyl-6-chlo- 581 8.98 D0 ryliurn perchlorate. robenzopyrylium perchlorate. 657 2. 98

3 2-p-methoxystyryl-5-phenyl-fi-chlorobenzopy- Discolored 2-p-methoxystyryl-3-phenylmethyl- 232 38; Do

i ryliurn perchlorate. benzopyrylium perchlorate. 652

4 Z-p-methoxystyryl-3-phenyl-6-methylbenzo- Discolored Z-p-methoxystyryl-B-phenylfi-chloro- 528 2.90 D

pyryllum perchlorate. benzopyrylium perchlorate. 658 6. 81

5 2-p-methoxystyryl-3-phenyl-6-methoxybenzo- Discolored Z-p-nitrostyryl-B-phenylbenzo- 456 9. 28 Vi 1 t pyrylium perchlorate. pyrylium perchlorate. 576 6.86 i o B '6 2-p-nitrostyryl-li'phenylbenzopyrylium Discolored Z-p-methoxystyryl-3-phenyl-6- 448 0.95 D

perchlorate. methoxybenzopyryliurn perchlorate. 579 8. 48

7 2-p-methoxystyryl-3-phenyl-6methylbenzo- Discolored 2-p-nitrostyryl-S-phenylbenzo- 567 6.13 Reddi h 1 I t pyryliurn perchlorate. pyrylium perchlorate. 640 8.38 i E V 0 e 8 2-p-nitrostyryl-3-phenylbenzopyrylium Discolored 2-p-rnethoxystyryl-3-phenyl-6- 567 7.56 }V. let perchlorate methylbenzopyrylium perchlorate. 648 1.22 10 9 Z-p-methoxystyryl-3-phenyl-fi-methoxybenzo- Dlscolored 2- -chlorostyryl3-phenylbenzo- 581 4. 62 }B1 ish vi'let pyrylium perchlorate. pyrylium perchlorate. 643 2. 65 u o 10 2-p-chlorostyryl-3-phenylhenzopyrylium Discolored 2-p-methoxystyryl-S-phenyl-G- 580 5.68 Do WW perchlorate H g I V p N methoxybenzopyrylium perchlorate. 650 2.85 p

Tgflrl] 1-Contlnued Compound structure Complex A max Color of dye Compounds belonging to Formula (I) Compounds belonging to Formula (II) (m /10 solution 11 2-p-methoxystyrylw'i-phenyl-ti-methylbenzo- Discolored 2-p-chlorostyryl-3-phenylbenzo- 4&5 63

- 571 5. 61 D0. pyryllum perchlorate. pyryhurn perchlorate. 643 3 80 12 2-p-chlorostyryl-3-phenylbenzopyrylium Discolored Q-p-methoxystyryl-3-phenyl-6- 569 7. 59 Do perchlorate. methylbenzopyrylium perchlorate. 647 3. 81 l3 2-p-ca.rboxystyryl-B-phenylbenzopyrylium Discolored 2-p-methoxystyryl-3- henyl-6- 514 2. 46 }Blue perchlorate. methoxybenzopyryllum perch orate. 654 8.60 14 Z-p-methoxystyryl-3-phenyl-6-methoxybenzo- Discolored 2-p-carboxystyryl-3-phenylbenzo- 510 2. 36 Do pyrylium perchlorate. pyr lium perchlorate. 654 8. 26 15 2-p-carboxystyryl-3-phenylbenzopyryllum Disco ored 2-p-rnethoxystyryl-li-phenyl-o- 536 3.11 D o perchlorate. methylbenzopyrylium perchlorate. 661 7. 46 16 2-p-methoxystyryl-3-12henyl-6-methy1bem0- Discolored 2-pcarboxysty'ryl-3-phenylbenzo- Do pyrylium perchlor e.

pyrylium perchlorate.

The present invention provides photosensitive mate- The color tone of the image developed on the photorials comprising a resinous binder solution for produc- 15 graphic recording material made of the photosensitive ing a photographic recording material wherein a dye sensitizer comprising either a benzopyrylium salt which is obtained according to the aforementioned synthetic method or its double complex salt dye sensitizer is utilized in the place of previously known dye sensitizers such as Rhodamine B or Styryl dye which have been used in conventional photographic recording materials. The supports, photo-active agents, vinyl monomers, and other materials such as solvents utilized in this invention are which have been conventionally employed. Binders utilized in this invention are not necessarily limited to water soluble resins, but include various kinds of resins and natural high polymeric substances. Typical examples include, cellulose acetate, cellulose acetate propionate, ethylcellulose, cellulose nitrate, polyvinylchloride, polyvinylidene chloride, polyvinylacetate, polyvinyl acetal, polyvinyl alcohol, polymethyl methacrylate, polystyrene, rubber hydrochloride, gelatin, casein, carboxymethyl cellulose gun arabic, etc. Useful photo-active agents (radical generators) include, in addition to the conventional aliphatic halides, such alicyclic compounds as benzene hexachloride, etc., and an aromatic halides such as polychlorobiphenyl, etc. Typical photo-active halides include those selected from the group consisting of chloroform, carbon tetrachloride, carbon tetrabromide, iodoform, hexachloroethane, hexachlorobenzene, tetrabromobutane, tetrachlorotetrahydronaphthalene and polychlorobiphenyl.

With respect to a photo-polymerizable N-vinyl monomer, any of monomers such as N-vinylindole, N- vinylcarbazole, N-vinyl-phenyl-a-naphthylamine, N- vinylpyrrole, N-vinylpyrrolidone, N- vinyldiphenylamine, N-vinylsuccinimide, N- vinylphthalimide, N-vinyl-N-phenylacetamide, N-vinyl- N-methylacetamide, N-vinyl-diglycollylimide and 3,o-dibromo-N-vinylcarbazole, can be used in the present invention.

Typical liquids which serve as solvents or dispersion media for use in the invention include water, methylethylketone, ethylacetate, acetone, toluene, trichloroethylene and methylalcohol.

According to the present invention, when a photosensitive material comprising a resinous binder solution containing the aforementioned resinous binder and photosensitive materials is applied to the surface of a support, made of film or paper to form a photosensitive layer, a transparent photosensitive film or photosensitive recording paper of light yellow light bluish violet color is obtained and its sensitivity is much better than conventional ones as seen from the examples.

material of the present invention wherein the photosensitive material prepared according to the present invention varies depending upon the kind of the resinous binder admixed with the aforementioned photosensitive materials. For instance, in case where gelatin is used as a resinous binder, the developed image takes on a color tone of deep reddish purple; in case where polystyrene, ethyl cellulose, cellulose nitrate, rubber hydrochloride, cellulose acetate, polyvinylchloride, celluslose acetate propionate and polyvinylidene chloride are used, the developed image devlops the color tone of greenish brown or blackish green. When polyvinyl acetate is used, the developed image presents the light brown color tone; and when polymethylmethacrylate is used, the developed image shows the color tone of light grey.

As for the composition of the photosensitive material according to the present invention, it is preferable to employ the resinous binder in the range between 50 and 100 parts by weight in a proper solvent, a photoactive agent between 5 and 100 parts by weight, and a dye sensitizer between 0.001 and 1.0 part by weight respectively per 100 parts by weight of N-vinyl monomer contained in said proper olvent.

DESCRIPTION OF THE PREFERRED EMBODIMENTS A number of Examples of the invention will now be described: Example I.

10 g of gelatin were dissolved uniformly in 50 ml of water at approximately 50C, to which 5 g of N- vinylcarbazole monomer (manufactured by Nippon Shokubai Kabushiki Kaisha or Japan Catalyst Mfg. Co., Ltd.) and 0.1 g of complex dye sensitizer No. l in Table 1 were added little by little and the mixture was stirred. After this solution was heated up to approximately C, 1 g of carbon tetrabromide was added to the solution and then it was stirred about two minutes. The suspension thus prepared was applied to the surface of a polyester film to form a light-yellow photosensitive layer of a thickness of 5 p. 10 u, and dried in the darkness to obtain a photographic recording material.

An original image was placed on this photographic recording material, and was exposed to the high voltage mercury lamp of 300 W for 30 seconds. it was then heated at a temperature between 60 and 70C for one minute. A deep reddish-purple image was formed thereon exactly opposite to those of the original image.

For comparison, a control photosensitive recording material was prepared according to the same method except for the use of Rhodamine B in the place of the dye sensitizer No. l. It'required about five minutes exposure to the light source to obtain the same density of the reproduced image as was obtained with the photosensitive recording material according to the present invention. 7

When any of bromoform, chlorofrom and iodoform were utilized in the place of carbon tetrabromide in the preparation of the aforementionedphotographic recording material according to this invention, the said TABLE 11 Composition of photosensitive material Expos- Color ing Color tone tone Resineus N-vmyl Photo-active Dye time of image nonimege Example binder (g.) monomer (g.) agent (g.) sensitizer (mg) Solvent (ml.) (see) area area Gelatin 3, 6-dibromoN-' Carbon tetra- No. 6 sensitizer Water (50) 25 Light Deep vinyl carbazole bromide (1.0) in Table 1 yellow reddish I v (5.0). purple. 6 Polyvinylidena 3,6-dibr0m0 N- Chloroform (1.0).. No.12 sensitizer Methyl ethyl 30 ..do Greenisli I chloride (5.0). z sirbyl earbazole in Table 1 ketone (20). brown. 7 Cellulose acetate 3, ti-dibromo-N- Iodoform (0.2)..-.. No. 13 sensitizer Ethyl acetate 30 Light Blaekish propionate (1.0). carbazole in Table 1 (5.0). (9.0). Y yellowish green.

. green.

result was obtained when a sheet of baryta paper was used as a support instead of the polyester film, a similar result was obtained. Example 2. i

5 g of polyvinylidene chloride weredissolved in 20 ml of methylethylketone, to which 5 g of N-vinyl carbazole monomer and 20 mg of the complex dye sensitizer No. 4 shown in Table-1. The same procedures were used as in Example 1 to obtain a photographic recording material. A greenish-brown image was produced in the photosensitive layer of the resultant photographic recording material when developed by the same method as that of Example Example 3.

l g of N-vinylcarbazole, 0.2 g of iodoform and 5 mg of the complex dye sensitizer No. 5 shown in Table-l were added to 10 g of 10 percent ethyl acetate solution of cellulose acetate propionate. The succeeding procedures were-as described in Example 1 to obtain a photographic recordingmaterial having a light yellowish green photosensitive layer. Another photographic recording material wasalso prepared by using the same quantity of bromoform instead of the aforementioned iodoform. These photographic recording materials respectively reproduced a blackish green image thereon whose density was the same as the one reproduced on the conventional photographic recording material in which Rhodamine Bwas used, despite the fact that the exposure was reduced by 1/5 to 1/10.

Example 4. v

The photographic recording materials were prepared by usingthe respective benzopyrylium salts obtained according to the aforementioned examples. (A) through (E) for preparing the benzopyrylium salts in the place of the respective complex dye sensitizers which were used as a-dye sensitizer in Examples 1 3 with similar conditions and procedures. The photographic recording materials thus prepared'showed sub- We claim: 1. A photosensitive material for producing a photographic recording material, comprising a resinous binder solution containing dispersed therein a .photo-polymerizable N-vinyl monomer, a photo-active wherein X is a radical selected from the group consisting of hydrogen, halogen, nitro radical and nitrile radical;

Y is a radical selected from the group'consisting of hydrogen, halogen, nitro radical, nitrile radical and carboxyl radical;

R is a radical selected from the group consisting of hydrogen and alkyl radicals having 1 m4 carbon atoms;

R is a radical selected from the group consisting of hydrogen and phenyl radical;

R and R each is a radical selected from the group consisting of hydrogen, alkyl radicals having 1 to 2 carbon atoms and alkoxyl radicals having 1 to 2 carbon atoms; n and n each is an integer of l to 2; and Z is an anionic functional group; and

(2) double complex salts consisting essentially of said benzopyrylium salt and a decolorized derivative having a chemical structure expressed by the formula-( ll) R! H )n' l 1 (:0-

H OCHB wherein X, Y, R,, R R R.,, n and n are as defined above.

2. A photosensitive material according to claim 1, in which said photo-polymerizable N-vinyl monomer is a member selected from the group consisting of N- vinylindole, N-vinylcarbazole, N-vinyl-phenyl-anaphthylamine, N-vinylpyrrole, N-vinylpyrrolidone, N-vinyldiphenylaminc, N-vinylsuccinimide, N- vinylphthaliumide, N-vinyl-N-phenylacetamide, N- vinyl-N-methylacctamide, N-vinyldigly-collylimide and 3,6-dibromo-N-vinylcarbazolei 3. A photosensitive material according to claim 1, in which said photo-active halide is selected from the group consisting of chloroform, carbon tetrachloride, carbon tetrabromide, iodoform, hexachloroethane, hexachlorobenzene, tetrabromobutane, tetrachlorotetrahydronaphthalene and polychlorobiphenyl, and the amount of said photo-active halide contained in said resinous binder solution is in the range of from 5 to 100 parts by weight per 100 parts by weight of said N-vinyl monomer contained in said resinous binder solution.

4. A photosensitive material according to claim 1, in which a resinous binder dissolved in said resinous binder solutions is a member selected from the group consisting of cellulose acetate, cellulose acetate propionate, ethylcellulose, cellulose nitrate, polyvinylchloride, polyvinylidene chloride, polyvinylacetate, polyvinyl acetal, polyvinyl alcohol, polymethyl methacrylate, polystyrene, rubber hydrochloride, gelatine, casein,, carboxymethyl cellulose and gum arabi, and a mixing ratio of said resinous binder against said N-vinyl monomer contained in said resinous binder solution is in the range of from 50 to 500 partsby weight per parts by weight of said N-vinyl monomer.

5. A photosensitive material according to claim 1, in which the amount of said salt dye sensitizer container in said resinous binder solution is in the range of from 0.001 to 1.0 part by weight per 100 parts by weight of said N-vinyl monomer contained in said resinous binder solution.

6. A photosensitive material according to claim 1, in which a solvent used in said resinous binder solution is a member selected from the group consisting of water, methylethylketone, ethylacetate, acetone, toluene, trichloroethylene and methyl-alcohol.

v UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,775, 130 Dated 7/73 Patent No.

Inventofls) "Iakamiti Enomoto 6t 1- It is certified that error appears in the above-identified patent and that said Letters Patent are hereby I corrected as shown below:

Column 1 the first formula should be deleted.

Signed and sealed this 16th day of April 19%.

(SLJAL) Attest:

EDWARD ILFLE'I'CIIERJR C. MARSHALL DANN Attesting Officer Commissioner of Patents FORM PO-1050 (10-69) 1 USCOMM-DC scan-P69 0.5. GOVERNMENT PRINTING OFFICE 2 l9 o-asc-su

Claims (5)

  1. 2. A photosensitive material according to claim 1, in which said photo-polymerizable N-vinyl monomer is a member selected from the group consisting of N-vinylindole, N-vinylcarbazole, N-vinyl-phenyl- Alpha -naphthylamine, N-vinylpyrrole, N-vinylpyrrolidone, N-vinyldiphenylamine, N-vinylsuccinimide, N-vinylphthaliumide, N-vinyl-N-phenylacetamide, N-vinyl-N-methylacetamide, N-vinyldigly-collylimide and 3,6-dibromo-N-vinylcarbazole.
  2. 3. A photosensitive material according to claim 1, in which said photo-active halide is selected from the group consisting of chloroform, carbon tetrachloride, carbon tetrabromide, iodoform, hexachloroethane, hexachlorobenzene, tetrabromobutane, tetrachlorotetrahydronaphthalene and polychlorobiphenyl, and the amount of said photo-active halide contained in said resinous binder solution is in the range of from 5 to 100 parts by weight per 100 parts by weight of said N-vinyl monomer contained in said resinous binder solution.
  3. 4. A photosensitive material according to claim 1, in which a resinous binder dissolved in said resinous binder solutions is a member selected from the group consisting of cellulose acetate, cellulose acetate propionate, ethylcellulose, cellulose nitrate, polyvinylchloride, polyvinylidene chloride, polyvinylacetate, polyvinyl acetal, polyvinyl alcohol, polymethyl methacrylate, polystyrene, rubber hydrochloride, gelatine, casein,, carboxymethyl cellulose and gum arabi, and a mixing ratio of said resinous binder against said N-vinyl monomer contained in said resinous binder solution is in the range of from 50 to 500 parts by weight per 100 parts by weight of said N-vinyl monomer.
  4. 5. A photosensitive material according to claim 1, in which the amount of said salt dye sensitizer container in said resinous binder solution is in the range of from 0.001 to 1.0 part by weight per 100 parts by weight of said N-vinyl monomer contained in said resinous binder solution.
  5. 6. A photosensitive material according to claim 1, in which a solvent used in said resinous binder solution is a member selected from the group consisting of water, methylethylketone, ethylacetate, acetone, toluene, trichloroethylene and methyl-alcohol.
US3775130A 1970-12-28 1971-12-23 Photosensitive material comprising benzopyrylium dye sensitizer Expired - Lifetime US3775130A (en)

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US3899338A (en) * 1972-02-09 1975-08-12 Horizons Inc Photosensitive material suitable for use as a photoresist
US4251619A (en) * 1977-06-08 1981-02-17 Konishiroku Photo Industry Co., Ltd. Process for forming photo-polymeric image
EP0223587A1 (en) * 1985-11-20 1987-05-27 The Mead Corporation Photosensitive materials containing ionic dye compounds as initiators
US4772530A (en) * 1986-05-06 1988-09-20 The Mead Corporation Photosensitive materials containing ionic dye compounds as initiators
US4800149A (en) * 1986-10-10 1989-01-24 The Mead Corporation Photohardenable compositions containing a dye borate complex and photosensitive materials employing the same
US4874450A (en) * 1987-01-29 1989-10-17 The Mead Corporation Laminating transparent or translucent materials using ionic dye-counter ion complexes
US4971891A (en) * 1987-10-13 1990-11-20 Fuji Photo Film Co., Ltd. Photopolymerizable compositions containing organoboron compounds and pyrylium or thiopyrylium dyes
US4977511A (en) * 1985-11-20 1990-12-11 The Mead Corporation Photosensitive materials containing ionic dye compound as initiators
US5418113A (en) * 1988-11-18 1995-05-23 Canon Kabushiki Kaisha Photosensitive resin composition and method of preparing volume type phase hologram member using same
US5616443A (en) 1993-08-05 1997-04-01 Kimberly-Clark Corporation Substrate having a mutable colored composition thereon
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US5681380A (en) 1995-06-05 1997-10-28 Kimberly-Clark Worldwide, Inc. Ink for ink jet printers
US5700850A (en) 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US5709955A (en) 1994-06-30 1998-01-20 Kimberly-Clark Corporation Adhesive composition curable upon exposure to radiation and applications therefor
US5721287A (en) 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5733693A (en) 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US5739175A (en) 1995-06-05 1998-04-14 Kimberly-Clark Worldwide, Inc. Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5747550A (en) 1995-06-05 1998-05-05 Kimberly-Clark Worldwide, Inc. Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5773182A (en) 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
US5782963A (en) 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5786132A (en) 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
US5798015A (en) 1995-06-05 1998-08-25 Kimberly-Clark Worldwide, Inc. Method of laminating a structure with adhesive containing a photoreactor composition
US5811199A (en) 1995-06-05 1998-09-22 Kimberly-Clark Worldwide, Inc. Adhesive compositions containing a photoreactor composition
US5837429A (en) 1995-06-05 1998-11-17 Kimberly-Clark Worldwide Pre-dyes, pre-dye compositions, and methods of developing a color
US5849411A (en) 1995-06-05 1998-12-15 Kimberly-Clark Worldwide, Inc. Polymer film, nonwoven web and fibers containing a photoreactor composition
US5855655A (en) 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5865471A (en) 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
US5885337A (en) 1995-11-28 1999-03-23 Nohr; Ronald Sinclair Colorant stabilizers
US5891229A (en) 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6008268A (en) 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
US6017661A (en) 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US6017471A (en) 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6033465A (en) 1995-06-28 2000-03-07 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6071979A (en) 1994-06-30 2000-06-06 Kimberly-Clark Worldwide, Inc. Photoreactor composition method of generating a reactive species and applications therefor
US6099628A (en) 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6242057B1 (en) 1994-06-30 2001-06-05 Kimberly-Clark Worldwide, Inc. Photoreactor composition and applications therefor
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6277897B1 (en) 1998-06-03 2001-08-21 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
US6368396B1 (en) 1999-01-19 2002-04-09 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6486227B2 (en) 2000-06-19 2002-11-26 Kimberly-Clark Worldwide, Inc. Zinc-complex photoinitiators and applications therefor
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US3899338A (en) * 1972-02-09 1975-08-12 Horizons Inc Photosensitive material suitable for use as a photoresist
US4251619A (en) * 1977-06-08 1981-02-17 Konishiroku Photo Industry Co., Ltd. Process for forming photo-polymeric image
US4977511A (en) * 1985-11-20 1990-12-11 The Mead Corporation Photosensitive materials containing ionic dye compound as initiators
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US4772530A (en) * 1986-05-06 1988-09-20 The Mead Corporation Photosensitive materials containing ionic dye compounds as initiators
US4800149A (en) * 1986-10-10 1989-01-24 The Mead Corporation Photohardenable compositions containing a dye borate complex and photosensitive materials employing the same
US4874450A (en) * 1987-01-29 1989-10-17 The Mead Corporation Laminating transparent or translucent materials using ionic dye-counter ion complexes
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US5418113A (en) * 1988-11-18 1995-05-23 Canon Kabushiki Kaisha Photosensitive resin composition and method of preparing volume type phase hologram member using same
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Also Published As

Publication number Publication date Type
DE2164395A1 (en) 1972-07-13 application
JPS509178B1 (en) 1975-04-10 grant
GB1378870A (en) 1974-12-27 application
DE2164395C3 (en) 1974-05-02 grant
FR2121030A5 (en) 1972-08-18 application
DE2164395B2 (en) 1973-10-11 application

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